1. Field of the Invention
The present invention relates to a positive resist composition and to a positive resist base material using the same.
2. Description of the Related Art
Lithographic processes requiring the definition in the vicinity of 0.25 xcexcm and using a chemically amplified positive resist have been launched in practical applications. Separately, with an increasing demand on semiconductor devices having reduced sizes, next-generation processes requiring fine patterns of from 0.13 xcexcm to 0.22 xcexcm using KrF excimer laser have been developed.
One of such conventional chemically amplified resists comprises a copolymer of p-vinylphenol and tert-butyl methacrylate as a resin ingredient (Japanese Unexamined Patent Application Publication No. 5-113667). The tert-butyl group in the resin is known as a typical acid-decomposable dissolution-inhibiting group but is insufficient in etching resistance. In next-generation processes, definition should further be improved by reducing the thickness of a resist (to 0.5 xcexcm or below) on an anti-reflection coating. However, the use of the tert-butyl group may further deteriorate dry-etching resistance in such a thinned resist film.
When a resist layer using the aforementioned resin is formed on an anti-reflection coating on a substrate, the anti-reflection coating prevents reflected light from the substrate, and an upper part of the resist layer is therefore overexposed as compared with the lower part thereof. In addition, the acid-decomposable dissolution-inhibiting group has weak hydrophobicity, and the resulting resist layer has an insufficient insolubilized surface layer. Accordingly, the top of the resulting patterned resist becomes round.
Additionally, this type of resins only has one acid-decomposable dissolution-inhibiting group in one molecule, and the resulting resist exhibits insufficient contrast between exposed portions and unexposed portions, has deteriorated definition and resist pattern profile and cannot be applied to further miniaturized semiconductor devices.
Accordingly, an object of the present invention is to provide a chemically amplified positive resist composition that can be applied to a resist having a reduced thickness, is excellent in dry-etching resistance and definition and can yield a patterned resist with a good profile (sectional shape).
The present inventors have found that the above objects can be achieved by using a positive resist composition comprising (A) a compound which generates an acid upon irradiation with active light or radiant ray, and (B) a resin which exhibits increased solubility in an alkali by action of an acid and includes a copolymer comprising (b-1) 40% to 85% by mole of a unit having an alkali-soluble group, (b-2) 3% to 25% by mole of a unit having (i) an acid-decomposable dissolution-inhibiting group and (ii) a group which accelerates dry-etching resistance, and (b-3) 3% to 40% by mole of a unit having an acid-decomposable dissolution-inhibiting group other than the units (b-1) and (b-2). The positive resist composition may further include a tertiary aliphatic lower amine, or an carboxylic acid, an oxoacid of phosphorus or a derivative thereof according to necessity. The present invention provides, in another aspect, a positive resist base material including a substrate, an anti-reflection coating formed on the substrate and having a predetermined thickness, and a resist layer formed on the anti-reflection coating, including the positive resist composition and having a predetermined thickness.
Ingredient (A)
The ingredient (A) for use in the present invention is an xe2x80x9cacid generatorxe2x80x9d, a compound which generates an acid upon irradiation with active light or radiant ray. The ingredient (A) is not specifically limited and can freely be selected from conventional acid generators such as iodonium salts, sulfonium salts, and other onium salts, oxime sulfonate compounds, bisalkyl-, biscycloalkyl- or bisaryl-sulfonyldiazomethanes, nitrobenzylsulfonates, iminosulfonates, and disulfones.
As the ingredient (A) for use in the present invention, an onium salt having a fluoroalkylsulfonate ion as an anion can advantageously be used. This type of onium salts generates an acid having higher strength and can sufficiently decompose the acid-decomposable dissolution-inhibiting group in the ingredient (B).
Cations constituting the onium salts include, for example, diphenyliodonium or triphenylsulfonium which may optionally have a substituent. Such substituents include methyl, ethyl, propyl, n-butyl, tert-butyl, and other lower alkyl groups; and methoxy, ethoxy, and other lower alkoxy groups.
Anions constituting the onium salts are fluoroalkylsufonate ions in which part or all of the hydrogen atoms of the alkyl moiety is fluorinated. The more carbon atoms the alkyl moiety has and the less the hydrogen atoms are fluorinated (the less the proportion of fluorine atoms in the alkyl moiety is), the less the strength as a sulfonic acid is. Accordingly, a fluoroalkylsulfonate ion, in which all the hydrogen atoms of an alkyl group having from 1 to 10 carbon atoms are fluorinated, is preferred.
Such onium salts are represented by following Formulae (I) and (II): 
wherein R1, R2, R3, R4 and R5 are each independently a hydrogen atom, an alkyl group having from 1 to 4 carbon atoms, or an alkoxy group having 1 or 2 carbon atoms; and Xxe2x88x92 is a fluoroalkylsulfonate ion.
Examples of the onium salts include, but are not limited to, trifluoromethanesulfonate or nonafluorobutanesulfonate of diphenyliodonium, trifluoromethanesulfonate or nonafluorobutanesulfonate of bis(4-tert-butylphenyl)iodonium, trifluoromethanesulfonate or nonafluorobutanesulfonate of triphenylsulfonium, trifluoromethanesulfonate or nonafluorobutanesulfonate of tri(4-methylphenyl)sulfonium, trifluoromethanesulfonate or nonafluorobutanesulfonate of tri(4-methoxyphenyl)sulfonium, trifluoromethanesulfonate or nonafluorobutanesulfonate of dimethylphenylsulfonium, and trifluoromethanesulfonate or nonafluorobutanesulfonate of methylcyclohexyl(2-oxocyclohexyl)sulfonium. Each of these onium salts can be used alone or in combination.
The amount of the ingredient (A) is from 0.5 to 20 parts by weight, and preferably from 5 to 15 parts by weight, relative to 100 parts by weight of the ingredient (B). If the amount of the ingredient (A) is out of this range, the resulting resist may not satisfactorily be patterned and may not yield a uniform resist solution.
Ingredient (B)
The ingredient (B) for use in the present invention is a resin which exhibits increased solubility in an alkali by action of an acid and includes a copolymer comprising (b-1) 40% to 85% by mole of a unit having an alkali-soluble group, (b-2) 3% to 25% by mole of a unit having (i) an acid-decomposable dissolution-inhibiting group and (ii) a group which accelerates dry-etching resistance, and (b-3) 3% to 40% by mole of a unit having an acid-decomposable dissolution-inhibiting group and being other than the units (b-1) and (b-2). The ingredient (B) has a weight average molecular weight (Mw) of preferably from 2000 to 15000 and more preferably from 3000 to 11000, a number average molecular weight (Mn) of preferably from 1000 to 10000 and more preferably from 1500 to 7000 and a molecular weight distribution (Mw/Mn) of preferably from 1.2 to 1.8 and more preferably from 1.3 to 1.7.
The unit (b-1) having an alkali-soluble group may be any unit having, for example, a phenolic hydroxyl group or a carboxyl group. The unit (b-1) may further have another substituent such as a lower alkyl group, as long as the alkali-solubility is not deteriorated. Examples of the unit (b-1) include a hydroxystyrene unit and xcex1-methylhydroxystyrene unit. By comprising 40% to 85% by mole, and preferably from 60% to 80% by mole, of the unit (b-1), the ingredient (B) exhibits appropriate alkali-solubility after exposure and can yield a resist pattern exhibiting satisfactory etching resistance and having a good sectional shape. An example of the unit (b-1) is a unit represented by the following structural formula: 
wherein Ra is a hydroxyl group or a carboxyl group; and R is a hydrogen atom or a methyl group. The substituent Ra is preferably substituted on the para-position, as the material is industrially advantageous and is easily available.
The unit (b-2) is a unit having both (i) an acid-decomposable dissolution-inhibiting group and (ii) a group which accelerates dry etching resistance. The ingredient (B) comprises from 3% to 25% by mole, and preferably from 5% to 20% by mole of the unit (b-2). By this configuration, the acid-decomposable dissolution-inhibiting group becomes insoluble in alkali in unexposed portions, and in contrast, is decomposed by action of an acid generated from the ingredient (A) in exposed portions, and the resulting exposed portions become soluble in alkali to pattern a resist. The unit (b-2) has the group (ii) which accelerates dry etching resistance, and the resulting resist film exhibits excellent dry etching resistance even when the thickness thereof is reduced.
Specific examples of the unit (b-2) are units derived from acrylic acid and having an ester group and (ii) a group which accelerates dry etching resistance on a carbon atom at the alpha position of the acrylic acid, which ester group comprises (i) an acid-decomposable dissolution-inhibiting group. More specifically, the unit (b-2) is preferably a unit represented by following Formula (III): 
wherein R7 is (ii) a group which accelerates dry etching resistance; and R6 is (i) an acid-decomposable dissolution-inhibiting group. The acid-decomposable dissolution-inhibiting group (i) is not specifically limited and includes any of groups known as acid-decomposable dissolution-inhibiting groups for use in chemically amplified resists.
Examples of the group R6 in Formula (III) include tert-butyl group, tert-amyl group, and other tertiary alkyl groups; 1-methylcyclohexyl group, 1-ethylcyclohexyl group, and other 1-alkyl-substituted monocycloalkyl groups; 2-methyladamantyl group, 2-ethyladamantyl group, and other 2-alkyl-substituted polycycloalkyl groups (2-alkyl-substituted bridged cyclic hydrocarbon groups); tert-butoxycarbonylmethyl (xe2x80x94CH2COO-tert-butyl) group, tert-amyloxycarbonylmethyl (xe2x80x94CH2COO-tert-amyl) group, tert-butoxycarbonylethyl (xe2x80x94C2H4COO-tert-butyl) group, tert-amyloxycarbonylethyl (xe2x80x94C2H4COO-tert-amyl) group, and other tertiary-alkyloxycarbonyl-alkyl groups; ethoxyethyl group, methoxypropyl group, and other chain alkoxy-substituted alkyl groups; tetrahydropyranyl group, tetrahydrofuranyl group, and other cyclic ether groups. Among them, tert-butyl group is typically preferred.
The group (ii) R7 which accelerates dry-etching resistance includes, for example, alicyclic hydrocarbon groups. Such alicyclic hydrocarbon groups have been proposed for use in ArF resists, are highly optically transparent to irradiated light or radiant ray and improve dry etching resistance of the resulting resists. The alicyclic hydrocarbon groups have high hydrophobicity in addition to dry etching resistance, therefore contribute to form a surface insoluble layer of the resist layer and can satisfactorily pattern the resist even on an anti-reflection coating.
The alicyclic hydrocarbon groups include, but are not limited to, organic groups each having a monocyclic cycloalkyl group or a polycyclic alicyclic hydrocarbon groups. Such monocyclic cycloalkyl groups include cyclopentyl and cyclohexyl groups. Rings constituting such polycyclic alicyclic hydrocarbon groups include, for example, spiroheptane ring, spirooctane ring, norbornane ring (corresponding to norbornyl group), adamantane ring (corresponding to adamantyl group), bornene ring, menthone ring (corresponding to menthyl group), menthane ring, thujane ring, sabinene ring, thujone ring, carane ring, carene ring, pinane ring, norpinane ring, bornane ring, fenchane ring, tricyclene ring, cholesterin ring, camphor ring, isocamphor ring, isobornane ring (corresponding to isobornyl group), diterpene rings, and triterpene rings. The organic group is a group connecting between the dry-etching resistance accelerating group and the alpha carbon of the acrylic acid and is not always necessary.
Among them, organic groups each having a bicycloalkyl group are preferred, of which isobornyloxymethylene group is typically preferred. A specifically preferred unit (b-2) is a unit derived from tert-butyl (xcex1-isobornyloxymethyl)acrylate.
The unit (b-3) having an acid-decomposable dissolution-inhibiting group is a unit having no alkali-soluble group as in the unit (b-1) and having an acid-decomposable dissolution-inhibiting group other than that of the unit (b-2). The acid-decomposable dissolution-inhibiting group in the unit (b-3) plays a similar role to that of the acid-decomposable dissolution-inhibiting group in the unit (b-2) and includes similar acid-decomposable dissolution-inhibiting groups as in the unit (b-2). Examples of the unit (b-3) are units represented by the following structural formula: 
wherein Rb is, for example, a tert-butyl group, tert-butoxycarbonylmethyl group, ethoxyethyl group, tetrahydropyranyl group, tetrahydrofuranyl group, or tert-butoxycarbonyl group; and R is a hydrogen atom or a methyl group.
By comprising 3% to 40% by mole, and preferably 5% to 25% by mole of the unit (b-3) in addition to the unit (b-2), the resulting ingredient (B) has two types of acid-decomposable dissolution-inhibiting groups in one molecule of the copolymer. In the formation of a fine pattern of a size of less than or equal to 140 nm, the resist composition comprising this copolymer exhibits higher contrast and more excellent definition and resist pattern profile than the case using a resin having one type of acid-decomposable dissolution-inhibiting group (protective group) in one molecule.
Among them, tert-butoxystyrene and other tertiary alkoxy-substituted styrene units are preferred as the unit (b-3) from the viewpoint of synthesis of the ingredient (B).
The resin ingredient as the ingredient (B) may be a copolymer further comprising conventional acrylic monomers, styrene or derivatives thereof as comonomer units in addition to the units (b-1), (b-2) and (b-3) within a range not deteriorating the objects of the present invention. The ingredient (B) can be synthetically prepared by, for example, a method described in Japanese Unexamined Patent Application Publication No. 11-171836.
Ingredient (C)
The tertiary aliphatic lower amine for use as the ingredient (C) is used for improving definition. Such tertiary aliphatic lower amines include, but are not limited to, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-tert-butylamine, tripentylamine, triethanolamine, and tributanolamine. Among them, triethanolamine and other trialkanolamines are preferred.
Ingredient (D)
To avoid tailing or tapering of the resulting resist on a thin film formed on a substrate, the resist composition may further comprise a carboxylic acid, an oxoacid of phosphorus or a derivative thereof according to necessity. Such thin films include, for example, silicon nitride (SiN, Si3N4 or SiON) films, TiN film and other nitrogen-containing thin films, phosphosilicate glass film (PSG) and other phosphorus-containing thin films, borosilicate glass film (BSG) and other boron-containing thin films, and borophosphosilicate glass film (BPSG) and other phosphorus-boron-containing thin films.
The carboxylic acid includes, but is not limited to, saturated or unsaturated aliphatic carboxylic acids, alicyclic carboxylic acids, aromatic carboxylic acids, and other carboxylic acids. Such saturated aliphatic carboxylic acids include, for example, formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, and other mono- or poly-carboxylic acids. The unsaturated aliphatic carboxylic acids include, for example, acrylic acid, crotonic acid, isocrotonic acid, 3-butenoic acid, methacrylic acid, 4-pentenoic acid, propiolic acid, 2-butynoic acid, maleic acid, fumaric acid, and acetylenecarboxylic acid. The alicyclic carboxylic acids include, for example, 1,1-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and 1,1-cyclohexanediacetic acid. The aromatic carboxylic acids include, for example, p-hydroxybenzoic acid, o-hydroxybenzoic acid (salicylic acid), 2-hydroxy-3-nitrobenzoic acid, phthalic acid, terephthalic acid, isophthalic acid, and other aromatic carboxylic acids each having a subsistent such as a hydroxyl group, nitro group or carboxyl group.
The oxoacid of phosphorus includes, but is not limited to, phosphoric acids, phosphorous acid and derivatives (e.g., esters) thereof such as phosphoric acid, phosphorous acid, di-n-butyl phosphate, and diphenyl phosphate; phosphonic acid and derivatives (e.g., esters) thereof such as phosphonic acid, dimethyl phosphonate, di-n-butyl phosphonate, phenyl phosphonate, diphenyl phosphonate, and dibenzyl phosphonate; phosphinic acid and derivatives (e.g., esters) thereof such as phosphinic acid and phenyl phosphinate. Among them, phenyl phosphonate is preferred.
The amounts of the ingredients (C) and (D) are each from 0.01% to 5% by weight and preferably from 0.1% to 2.0% by weight relative to the weight of the ingredient (B). If the amounts of these ingredients exceed the above range, the resulting resist may not satisfactorily be patterned. If the amounts are less than the above range, the advantages of the addition of the ingredients (C) and (D) may not be exhibited, thus inviting tailing or tapered profile.
Positive Resist Base Materials
The positive resist composition of the present invention may be directly formed on a substrate. Preferably, an organic or inorganic anti-reflection coating having a thickness of 30 to 200 nm is formed on the substrate, and a resist film having a thickness of 200 to 500 nm is then formed on the anti-reflection coating using the positive resist composition of the present invention. The resulting resist base material can pattern the resist with a good shape and high definition, and the patterned resist is highly resistant to etching. The anti-reflection coating is preferably an organic anti-reflection coating prepared by using, for example, an coating composition for an anti-reflection coating such as xe2x80x9cBC-K037xe2x80x9d (trade name; available from Tokyo Ohka Kogyo Co., Ltd.). This type of anti-reflection coating can satisfactorily inhibit reflection of irradiated light or radiant ray from the substrate. When the resist layer is formed on this anti-reflection coating, an insolubilized surface layer derived from the unit (b-2) of the ingredient (B) is formed, and the resulting patterned resist has a good shape.
The present invention will be illustrated in further detail with reference to several examples and comparative examples below, which are not intended to limit the scope of the invention.